JPH03106890A - Silyl derivative of 2-allyl phenol - Google Patents

Abstract

NEW MATERIAL: A compound of the formula (R¹-R³ are each C_1-8 hydrocarbon).

EXAMPLE: (2-Allyl)phenoxytrimethyl-silane.

USE: Useful as comonomers for copolymerization with a lower olefin such as propylene. They are also useful for the introduction of functional sites into copolymers produced.

PROCESS: Sodium chunks are added to a mixture of 2-allylphenol and toluene at 0°C under atmosphere of inert gas. The mixture is reacted and THF is added. The reaction mixture is stirred at room temperature overnight and then heptane is added. After removal of the precipitate, low boiling components are removed from the solution. The remaining solution is distilled in vacuo to give the exemplified compound.

COPYRIGHT: (C)1991,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel silyl derivatives of certain substituted phenols, particularly silyl derivatives of 2-allylphenol. In particular, the present invention provides the following formula, (in the above formula, Rl, R! and R3 independently have 1 to about 8 carbon atoms.
linear, branched, and cyclic hydrocarbon groups). 2. (2-allyl)phenoxytriisopropylsilane. 3. (2-allyl)phenoxydimethylphenylsilane. 4. (2-allyl)phenoxydiphenylmethylsilane. (In the above formula, Rl, R-value and Rs independently have 1 to about 8 carbon atoms.
(selected from linear, linear, and cyclic hydrocarbon groups). European Patent Application No. 88900936.1 (corresponding PC
T International Publication Na WO88/08856. November 17, 1988) and our co-pending patent application no.
No. 7,895, the oxygen of a copolymerizable hydroxy-containing compound is protected by replacing the hydrogen of said hydroxy-containing compound with a silyl group having minimal steric bulk, i.e., having at least about 3 carbon atoms in its surroundings. It is disclosed that a comonomer for brobylene can be prepared by the following methods. The compound 2-allylphenol is known. A silylated monomer of the following formula, where I×÷ is a divalent bonding group, is used for propylene for the introduction of functional sites into cobolymers produced by Ziegler-Natta catalysts in our above-mentioned co-pending application. It has been suggested as a comonomer for The unique advantages of 2-allylphenol as a possible comonomer in its silylated form are not seen in the prior art and this monomer is considered novel as a compound. The present invention is based on the following formula, (In the above formula, RI, R! and R3 independently have 1 to about 8 carbon atoms.
It is a new compound selected from linear, cyclic, and cyclic hydrocarbon groups. This includes (2-allyl)phenoxytriisopropylsilane, (2-allyl)phenoxydimethylphenylsilane, (2-allyl)phenoxydiphenylmethylsilane, (2-allyl)phenoxytrinotylsilane, and (2-allyl)phenoxytrinotylsilane. Contains enoxytriethylsilane. Below are examples of the preparation of compounds within the above formula. Mato: Synthesis of (2-allyl)phenoxytrimethylsilane All operations were performed under an inert atmosphere using the standard Schlenk method. All liquid reagents and solvents were purged with inert gas before being introduced into the reaction system. A 1000II1 round bottom flask with an argon population was charged with 58.36 g (0.435 moles) of 2-allylphenol followed by 150 jd of toluene. The mixture was cooled to 0°C and 10.07 g (0.438
mol) was added three times. 1.5 from the last sodium addition
After an hour, the cooling bath was removed, Nacj! Stirring of the mixture was stopped due to the formation of a precipitate, and after 2 hours, 50 d of tetrahydrofuran was added. This mixture was stirred at room temperature overnight.

Then 42,511 liters of hebutane was added and the precipitate was allowed to settle for 2 hours. The mixture was filtered through a glass filter to obtain a clear golden solution. Low-boiling components were removed by atmospheric distillation up to a temperature of 120°C. 1 by vacuum distillation of the remaining solution
We obtained a major precept that evaporates at 30-132°C (2 mHg). The main product collected showed a yield of 63% and was characterized by 'HNMR and GCS.

Part 1: (2-allyl)phenoxytriisopropylsilane was produced using the method described in Example 1. 11=(2-allyl)phenoxydiphenylmethylsilane was prepared using the synthesis method described in Example 1.

For copolymerization of monomers such as lower olefins such as propylene, standard inert atmosphere methods were used to remove moisture and oxygen throughout the following operations.

Volume given in a round bottom flask with side arm, magnetic stir bar and stopper (the apparatus was assembled hotter than the drying oven and evacuated and filled with inert gas several times or purged with inert gas for at least 15 minutes) (Usually 1
25d) solvent (heptane or toluene) was added. The solvent was sodium and triethylaluminum (TI
! A) Freshly distilled under reflux under an inert atmosphere for at least 18 hours. Immediately after adding the solvent to the flask, add the alkyl aluminum cocatalyst (approximately 25-t% hebutane solution (
0.715 g/hebutane d)) was added to the flask, lowered into a thermostatic oil bath and magnetic stirring started.

At this point, the inert gas in the flask was replaced with gaseous comonomer (propylene or ethylene) by evacuation and returning to atmospheric pressure with comonomer a minimum of three times. This 3
After two cycles, the solution is stirred for at least 10 minutes;
The solvent was saturated with comonomer. The pressure was maintained at approximately 1 atm. Next, an "external donor", usually diphenyldimethoxysilane or phenyltriethoxysilane, is added. Polymerization was initiated by addition of a transition metal-containing cocatalyst (titanium tetrachloride on a magnesium chloride support). Once the gaseous comonomer was consumed, it was replaced by maintaining the pressure at 1 atm. After a predetermined time (usually about 2 hours), the reaction was quenched by addition of acidic alcohol (HCI in isopropanol, ethanol, and/or methanol). The quenched reaction slurry was mixed with a volume of alcohol solution at least twice the initial volume of inert reaction solvent. The resulting slurry was stirred for at least 45 minutes and then filtered. This treatment not only stops the reaction, but also dissolves catalyst residues, removes silyl groups, and thus regenerates hydroxyl groups. If filtration is progressing very slowly, mix the slurry with enough water to allow filtration to proceed at a convenient rate. The polymer is resuspended in alcohol, stirred, filtered,
Vacuum dried overnight. The soluble content of boiling hebutane was determined by standard methods. fii: 500 Jd with propylene and (2-allyl) phenoxytrinotylsilane copolymerized side arm! The round bottom flask was evacuated and filled with argon three times. To this flask was added 3.5% of dried, degassed hebutane, followed by (2-allyl)phenoxytrinotylsilane. 8 d (0.018 mol) was added. This solution was saturated with propylene and triethylaluminum cocatalyst (0.715 g/heptane d
) 5.3M1 was added to the flask. The mixture was then placed in an oil bath kept at 50°C and 0.095 g of titanium cocatalyst (initiating polymerization) was added. The reaction was allowed to proceed for 2 hours, after which about 300 lI1 of acidic isopropanol
The mixture was quenched by the addition of .

Stirring of the alcoholic suspension was continued for about 1 hour, after which the green bottoms were filtered and the polymer was resuspended in isopropanol with stirring for about 1.5 hours. The raw bottom material is then filtered,
Vacuum dried.

Claims (1)

[Claims] 1. The following formula▲ includes mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, R^1, R^2 and R^3 independently have a carbon number of 1
~8 linear, branched, and cyclic hydrocarbon groups). 2, (2-allyl)phenoxytriisopropylsilane. 3, (2-allyl)phenoxydimethylphenylsilane. 4, (2-allyl)phenoxydiphenylmethylsilane. 5, (2-allyl)phenoxytrimethylsilane. 6, (2-allyl)phenoxytriethylsilane.